EP0479031B1 - Harzmischung, ihre Herstellung und eine mehrschichtige Struktur - Google Patents
Harzmischung, ihre Herstellung und eine mehrschichtige Struktur Download PDFInfo
- Publication number
- EP0479031B1 EP0479031B1 EP91115737A EP91115737A EP0479031B1 EP 0479031 B1 EP0479031 B1 EP 0479031B1 EP 91115737 A EP91115737 A EP 91115737A EP 91115737 A EP91115737 A EP 91115737A EP 0479031 B1 EP0479031 B1 EP 0479031B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- evoh
- water
- phyllosilicate
- layer
- resin composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000011342 resin composition Substances 0.000 title claims description 20
- 238000000034 method Methods 0.000 title claims description 15
- 230000008569 process Effects 0.000 title claims description 11
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 claims description 78
- 239000004715 ethylene vinyl alcohol Substances 0.000 claims description 75
- 229910052615 phyllosilicate Inorganic materials 0.000 claims description 42
- 239000000203 mixture Substances 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 12
- 239000005977 Ethylene Substances 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 2
- 239000010410 layer Substances 0.000 description 32
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 17
- 229910052901 montmorillonite Inorganic materials 0.000 description 17
- -1 polyethylene Polymers 0.000 description 17
- 230000004888 barrier function Effects 0.000 description 15
- 239000007789 gas Substances 0.000 description 15
- 239000008188 pellet Substances 0.000 description 14
- 239000002356 single layer Substances 0.000 description 14
- 229920005989 resin Polymers 0.000 description 10
- 239000011347 resin Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 239000004743 Polypropylene Substances 0.000 description 9
- 229920001155 polypropylene Polymers 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000006185 dispersion Substances 0.000 description 8
- 229910052618 mica group Inorganic materials 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
- 235000013305 food Nutrition 0.000 description 6
- 239000010445 mica Substances 0.000 description 6
- 238000004806 packaging method and process Methods 0.000 description 6
- 238000007127 saponification reaction Methods 0.000 description 6
- 229920005992 thermoplastic resin Polymers 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000004698 Polyethylene Substances 0.000 description 5
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 5
- 238000010348 incorporation Methods 0.000 description 5
- 229920000573 polyethylene Polymers 0.000 description 5
- 239000012790 adhesive layer Substances 0.000 description 4
- 239000004840 adhesive resin Substances 0.000 description 4
- 229920006223 adhesive resin Polymers 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000002274 desiccant Substances 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 238000004898 kneading Methods 0.000 description 4
- 238000003475 lamination Methods 0.000 description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 4
- 239000000155 melt Substances 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000006359 acetalization reaction Methods 0.000 description 3
- 150000008064 anhydrides Chemical class 0.000 description 3
- 239000002734 clay mineral Substances 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 229910021647 smectite Inorganic materials 0.000 description 3
- 239000000454 talc Substances 0.000 description 3
- 229910052623 talc Inorganic materials 0.000 description 3
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 239000000440 bentonite Substances 0.000 description 2
- 229910000278 bentonite Inorganic materials 0.000 description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 2
- 239000000378 calcium silicate Substances 0.000 description 2
- 229910052918 calcium silicate Inorganic materials 0.000 description 2
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920001083 polybutene Polymers 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- 229910018516 Al—O Inorganic materials 0.000 description 1
- 229910019092 Mg-O Inorganic materials 0.000 description 1
- 229910019395 Mg—O Inorganic materials 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- NOZAQBYNLKNDRT-UHFFFAOYSA-N [diacetyloxy(ethenyl)silyl] acetate Chemical compound CC(=O)O[Si](OC(C)=O)(OC(C)=O)C=C NOZAQBYNLKNDRT-UHFFFAOYSA-N 0.000 description 1
- XBJMDQNMFHPWHO-UHFFFAOYSA-N [ethenyl-di(propanoyloxy)silyl] propanoate Chemical compound CCC(=O)O[Si](OC(=O)CC)(OC(=O)CC)C=C XBJMDQNMFHPWHO-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- VNSBYDPZHCQWNB-UHFFFAOYSA-N calcium;aluminum;dioxido(oxo)silane;sodium;hydrate Chemical compound O.[Na].[Al].[Ca+2].[O-][Si]([O-])=O VNSBYDPZHCQWNB-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 238000009820 dry lamination Methods 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- ZLNAFSPCNATQPQ-UHFFFAOYSA-N ethenyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C=C ZLNAFSPCNATQPQ-UHFFFAOYSA-N 0.000 description 1
- 229920006244 ethylene-ethyl acrylate Polymers 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910000271 hectorite Inorganic materials 0.000 description 1
- KWLMIXQRALPRBC-UHFFFAOYSA-L hectorite Chemical compound [Li+].[OH-].[OH-].[Na+].[Mg+2].O1[Si]2([O-])O[Si]1([O-])O[Si]([O-])(O1)O[Si]1([O-])O2 KWLMIXQRALPRBC-UHFFFAOYSA-L 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000010102 injection blow moulding Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000010128 melt processing Methods 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 1
- 235000019799 monosodium phosphate Nutrition 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- UTSYWKJYFPPRAP-UHFFFAOYSA-N n-(butoxymethyl)prop-2-enamide Chemical compound CCCCOCNC(=O)C=C UTSYWKJYFPPRAP-UHFFFAOYSA-N 0.000 description 1
- DCBBWYIVFRLKCD-UHFFFAOYSA-N n-[2-(dimethylamino)ethyl]-2-methylprop-2-enamide Chemical compound CN(C)CCNC(=O)C(C)=C DCBBWYIVFRLKCD-UHFFFAOYSA-N 0.000 description 1
- 229910000273 nontronite Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910000275 saponite Inorganic materials 0.000 description 1
- 229910000276 sauconite Inorganic materials 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229940048086 sodium pyrophosphate Drugs 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- 238000003856 thermoforming Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 1
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
- 235000019801 trisodium phosphate Nutrition 0.000 description 1
- 229910052902 vermiculite Inorganic materials 0.000 description 1
- 239000010455 vermiculite Substances 0.000 description 1
- 235000019354 vermiculite Nutrition 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
Definitions
- the present invention relates to a resin composition used for films or containers for packaging food and the like and having high transparency, gas barrier property and processability.
- the present invention also relates to a process for producing the above resin composition and to a multilayered structure comprising at least one layer of this composition.
- ethylene-vinyl alcohol copolymer (hereinafter referred to as "EVOH”) is a thermoplastic melt-processable resin having excellent gas barrier property, oil resistance and odor-keeping property as compared to other resins and has hence been suitably used in the form of shaped articles such as film, sheet and container, particularly for packaging food.
- EVOH however has the drawback that the properties of its shaped articles greatly change when ambiant conditions such as humidity and temperature change and in particular their gas barrier properties are largely influenced by absorption of moisture and lower under highly humid conditions.
- JP-A-173038/1985, 28661/1985 and 207338/1987 disclose that the moisture absorbency of EVOH is decreased by laminating a low-water-absorbent resin such as polyethylene or polypropylene onto an EVOH film or sheet;
- JP-A-2191/1980 and 65378/1978 disclose improvement of resistance to moisture absorption by acetalization of the surface of an EVOH film or sheet;
- JP-A-43554/1989 US-A-4,818,782
- EP-A-301 878 disclose improvement of gas barrier property by incorporating water-nonswellable mica into EVOH in the nonaqueous or aqueous system.
- the above method of lamination however requires a costly lamination operation and the laminated article obtained absorbs moisture gradually to lower the gas barrier property of EVOH, thus being far from substantial solution. Furthermore, with respect to retort treatment, which has been widely used in recent years, shaped articles from such laminate still absorb moisture when retorted, decreasing their gas barrier properties.
- the above method of acetalization newly requires a treatment process for the acetalization of EVOH that has once been formed into film or sheet, thus being economically disadvantageous. Incorporation of mica into EVOH should be in a large amount to ensure a sufficient gas barrier property and then gives compositions having opaque appearance.
- US-A-4,425,410 discloses melt kneading a drying agent such as bentonite with EVOH, thereby preventing the gas barrier property from deteriorated by retort treatment; and JP-A-242841/1986 discloses incorporating an inorganic filler such as non-water-swellable talc into EVOH to increase flexural modulus and thermal deformation temperature.
- JP-A-253442/1989 discloses, for a multilayered structure comprising a layer of a blend of EVOH and polyamide and a layer of a hydrophobic thermoplastic resin, incorporating a filler such as calcium silicate into the above blend layer.
- This literature does not describe incorporation of such filler in the presence of water.
- JP-A-308627/1989 discloses, for a multilayered structure comprising a blend layer of EVOH and mica and a blend layer of other thermoplastic resin and mica, incorporating a filler such as calcium silicate into the above blend layer, but the document equally fails to describe the incorporation being conducted in the presence of water.
- an object of the present invention is to provide a resin composition having excellent gas barrier property even under highly humid conditions without decreasing the good transparency inherent to conventional EVOH to a great extent.
- Another object of the present invention is to provide a multilayered structure by utilizing ready laminatability of the above resin composition with other thermoplastic resin layer, which is very useful as packaging material e.g. for food.
- the above object can be achieved by providing a resin composition comprising an ethylene-vinyl alcohol copolymer (EVOH) having an ethylene content of 20 to 60 mol% and a water-swellable phyllosilicate, said water-swellable phyllosilicate being dispersed in the EVOH with a basal spacing satisfying the following condition (I) (x - y) ⁇ 2 wherein x represents the basal spacing in angstrom of the water-swellable phyllosilicate dispersed in EVOH and y represents the basal spacing in angstrom of dry powder of the water-swellable phyllosilicate.
- EVOH ethylene-vinyl alcohol copolymer
- the EVOH used in the present invention is obtained, representatively, by saponifying an ethylene-vinyl acetate copolymer and has an ethylene content of 20 to 60 mol%, preferably 25 to 55 mol%.
- an ethylene content of less than 20 mol% the resistance to water and moisture decreases, the gas barrier property under highly humid conditions decreases, the resistance to stress cracking decreases and the good melt processability becomes difficult to maintain.
- an ethylene content exceeding 60 mol% the gas barrier property decreases although the resistance to water and moisture is improved. In both cases, the resultant EVOH'S are not suited for packaging purposes.
- the saponification degree of vinyl acetate component be at least 95 mol%, preferably at least 98 mol%. If the saponification degree is less than 95 mol%, the thermal stability will become worse, thereby creating tendency to generate gels upon melt processing, and further the gas barrier property and oil resistance will decrease. Then, the EVOH cannot maintain its inherent characteristics or produce the effect of the present invention.
- a silicon-containing EVOH having an ethylene content of 20 to 60 mol%, a saponification degree of vinyl acetate component of at least 95 mol% and a vinyl silane content of 0.0001 to 0.5 mol% can also be used.
- the vinyl silane can be introduced by using an olefinically unsaturated monomer containing silicon.
- Known monomers such as those disclosed in JP-A-290046/1986 can be used for this purpose, and their examples are vinyltrimethoxysilane, vinylmethyldimethoxysilane, vinyltriacetoxysilane and vinyltripropionyloxysilane.
- the vinyl silane content is, while depending on the intended purpose, preferably 0.0001 to 0.5 mol%, more preferably 0.001 to 0.1 mol%.
- the EVOH may have any melt index (determined at a temperature of 190°C and under a load of 2160 g; hereinafter referred to as "MI") but has generally one of 0.1 to 50 g/10 min. Further the EVOH referred to in the present invention may have been modified with a small amount of a copolymerizable monomer.
- MI melt index
- modifying monomer examples include propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, acrylates, methacrylates, maleic acid, phthalic acid, itaconic acid, higher aliphatic acid vinyl esters, alkyl vinyl ethers, N-vinylpyrrolidone, N-n-butoxymethylacrylamide, N-(2-dimethylaminoethyl)methacrylamide and quaternary compounds thereof and N-vinylimidazole and quaternary compounds thereof.
- the water-swellable phyllosilicate used in the present invention and to be dispersed in EVOH is now described.
- the representative structure of the phyllosilicate is a multilayered phyllosilicate comprising a unit consisting of a layer of a sheet-like structure of Si-O tetrahedron and one of Al-O or Mg-O octahedron laminated with each other (hereinafter this unit is referred to as "flake").
- the size of a flake which is a unit constituting the phyllosilicate, has an average size of not more than 1 ⁇ m and the basal spacing, i.e. distance between adjacent flakes, is not more than 20 angstroms.
- the water-swellability as referred to herein of the water-swellable phyllosilicate is the property of incorporating water as a coordination compound, or absorbing water, to swell and in some cases allowing the flakes or parts thereof to disperse to form a colloid.
- the basal spacing of a water-swellable phyllosilicate dispersed in EVOH satisfy the following condition (I) (x - y) ⁇ 2 wherein x represents the basal spacing in angstrom of the water-swellalble phyllosilicate dispersed in EVOH and y represents the basal spacing in angstrom of dry powder of the water-swellable phyllosilicate.
- x and y are determined by the measurement of basal spacing by X-ray diffraction method.
- the water-swellable phyllosilicate be uniformly dispersed in EVOH.
- the condition of "uniform dispersion” herein means that no or only trace of local lumps are, with an optical microscope (magnification: 10) observed on the surface and cross section of a film obtained by melt casting an EVOH composition containing a phyllosilicate.
- water-swellable phyllosilicate examples include clay minerals such as smectite and vermiculite and synthetic micas. Concrete examples of smectite are montmorillonite, beidellite, nontronite, saponite, hectorite, sauconite and stevensite. These minerals may either be natural or synthetic. Preferred among the above is smectite, in particular montmorillonite. It is preferred for the purpose of uniform dispersion and incorporation into EVOH that the phyllosilicate used be in the colloidal state of aqueous sol. The above phyllosilicates may be used singly or in combination.
- the phyllosilicate is contained in EVOH in an amount of 0.05 to 30% by weight based on the weight of EVOH, preferably 0.1 to 15% on the same basis, more preferably 1 to 10% on the same basis. If the content of the phyllosilicate is less than 0.05% by weight, the gas barrier property of the resulting composition will not be improved very much. On the other hand if the content exceeds 30% by weight, the melt viscosity will increase and the transparency will decrease markedly, both of which are not preferred.
- the above dispersion state is achieved, representatively, by mixing EVOH having an ethylene content of 20-60 mol% and a water-swellable phyllosilicate in the presence of water and then drying the mixture. More concretely, to a colloidal phyllosilicate dispersion in a dispersant of water is added an alcohol such as methyl alcohol, n-propyl alcohol or isopropyl alcohol and, if necessary, water, and then EVOH, the mixture is heated with stirring to dissolve EVOH, and the obtained solution is solidified by cooling, followed by crushing and drying to give pellets.
- an alcohol such as methyl alcohol, n-propyl alcohol or isopropyl alcohol
- EVOH is dissolved with heating in the above alcohol/water mixed solvent or the like, then a phyllosilicate is added to the solution and the resulting mixture is stirred, cooled to solid, followed by crushing and drying to give pellets.
- the above EVOH solution is mixed and stirred with a colloidal phyllosilicate dispersion forming a sol in a dispersant of water, the above alcohol/water mixed solvent or the like, and the mixture is cooled to solid, followed by crushing and drying to pellets.
- a process which comprises first preparing by the above process an aqueous composition, such as an EVOH solution containing a phyllosilicate in a high concentration, and then further dissolving EVOH and kneading with it.
- an aqueous sol of a phyllosilicate may be added dropwise to a melt of EVOH at a temperature above its melting point to effect kneading using a melt kneader such as bent-type melt kneader.
- the drying of the mixture of EVOH and phillosilicate can be conducted either by forced system or by air drying, where it is preferred that the conditions be so selected as to minimize the amount of remaining solvent (water or water/alcohol).
- the resin composition of the present invention may incorporate other thermoplastic resin, filler, drying agent, antistatic agent and the like, within limits not to impair the purpose of the present invention.
- incorporation of a drying agent is often desirable.
- the drying agent to be used are hydrate-forming salts, i.e. salts that absorb water as crystallization water; such as phosphates, e.g.
- sodium dihydrogenphosphate disodium hydrogenphosphate, trisodium phosphate, trilithium phosphate and sodium pyrophosphate, and anhydrides of the foregoing, other hydrate-forming salts, such as sodium borate and sodium sulfate, and anhydrides thereof; other hygroscopic compounds such as sodium chloride, sodium nitrate, sugar and silica gel; and super-absorbent resins.
- the resin composition of the present invention is used as a single-layer film or at least one layer, in particular intermediate layer, of multilayered structures, for solution coating purpose and the like.
- the resin composition can be processed into films by known processes with no specific limitation.
- the layer of the resin composition of the present invention can be laminated with any resin layer.
- the other resin used for the layer laminated are thermoplastic resins, in particular those having resistance to moisture absorption, e.g.
- polyolefins such as polyethylene, polypropylene and polybutene, copolymers principally containing an olefin, polystyrene, polyethylene terephthalate, polycarbonates, polyamides such as 6 nylon and 66 nylon, and mixtures of the foregoing.
- Polyethylene, polypropylene and their mixtures are particularly suitably used among the above resins.
- the resin composition of the present invention can readily be laminated with the above thermoplastic resins. Lamination with these resins protects and reinforces the layer of the resin composition of the present invention and prevents its gas barrier property from deterioration under high humidity, as well as provides excellent mechanical properties.
- any adhesive resin can be used insofar as it assures no delamination during use, and its preferred examples are olefinically modified polymers containing carboxyl groups, which are obtained by chemically, e.g. addition and grafting, bonding an unsaturated carboxylic acid or its anhydride to an olefin polymer such as polyethylene, polypropylene or polybutene or a copolymer principally containing olefin.
- the adhesive resin are polyethylene modified by grafting maleic anhydride, polypropylene modified by grafting maleic anhydride, ethylene-ethyl acrylate copolymer modified by grafting maleic anhydride and ethylene-vinyl acetate copolymer modified by grafting maleic anhydride.
- These adhesive resins may be used singly or in combination, or, within a limit not to damage the effect of the present invention, may be mixed with EVOH.
- Multilayered structures comprising at least one layer of the resin composition of the present invention can be prepared by any known process and its examples are co-extrusion, melt coating, extrusion lamination and dry lamination.
- the resin composition of the present invention can be processed, as a single-layer or multilayered structure, into films, sheets, tubes, cups, bottles and the like, by known processes such as thermoforming, injection molding, blow molding and stretching blow molding.
- the shaped articles thus obtained are suitably used as containers for foods in general, foods for retorting and medicines.
- the above-described aqueous composition containing as essential components EVOH, phyllosilicate and water may be casted into films, or formed into multilayered structures by coating on a base material (e.g. film, sheet and container such as cup or bottle), followed by drying.
- a base material e.g. film, sheet and container such as cup or bottle
- the aqueous composition may be in the form of solution or dispersion.
- the solution is desirably obtained by the use of a solvent for EVOH, such as water/alcohol mixed solvent.
- the haze as determined by JIS-K6714 of single-layer films obtained from the resin composition of the present invention is not more than 25%, generally not more than 20% and in most cases not more than 15%.
- MI Melt index
- OX-TRAN 10/50 A was used and the OTR was measured at 20°C, 85% RH and 100% RH.
- a film each was prepared from a specimen EVOH composition containing a phyllosilicate and its surface and section were observed with an optical microscope (magnification: 10) for aggregates or local lumps of the phyllosilicate.
- a specimen film was measured for haze in accordance with JIS K6714 using a haze meter manufactured by Nihon Seimitsu Kogaku Co.
- Specimen EVOH pellets containing montmorillonite were calcined and the content was calculated from the weight of the residue.
- X-ray diffractometer manufactured by Rigaku Denki Co. was used to test a film obtained by melt casting a specimen EVOH composition containing a phyllosilicate and the phyllosilicate powder treated at 50°C for 48 hours in the air. The basal spacing of these were determined and the difference, x - y, of the two were calculated, wherein x is the basal spacing in angstrom of the water-swellalble phyllosilicate uniformly dispersed in EVOH and y is the basal spacing in angstrom of dry powder of the water-swellable phyllosilicate.
- the term "part" means "part by weight”.
- a vessel with a stirrer was charged with water and 1 part of montmorillonite (Kunipia-F, made by Kunimine Kogyo Co.) to a concentration of 5% by weight, and the contents were stirred to give a colloidal montmorillonite.
- montmorillonite Korean No. 845, Kunimine Kogyo Co.
- To this colloid added were 99 parts of an EVOH having an ethylene content of 32 mol%, a saponification degree of vinyl acetate component of 99.5 mol% and an MI of 4.4 g/10 min, methyl alcohol and water in such amounts as to adjust the concentrations of EVOH and methyl alcohol to 10% by weight and 65% by weight respectively.
- the mixture was heated with stirring to dissolve EVOH and give a mixed solution of montmorillonite and EVOH.
- the vessel containing the solution was cooled in ice water to solidify the solution, and the solidified matter was crushed through a mixer and dried preliminary at 50°C for a time and then at 105°C for 12 hours.
- the thus dried matter was extruded through an extruder at 240°C into pellets comprising the EVOH and montmorillonite. Part of the pellets thus obtained were then extruded through an extruder connected with a T-die at a die temperature and a cylinder temperature of both 230°C to give a single-layer film.
- a 3-kind/5-layer multilayered sheet with an intermediate layer from the pellets was prepared through the combination of an extruder having a branched melt channel for inner and outer layers, an extruder for intermediate layer and an extruder having a branched melt channel for adhesive layers, and a T-die.
- the resins used for the molding were the above pellets for intermediate layer, polypropylene (Noblen PY220, made by Mitsubishi Petrochemical Co.) for inner and outer layers and a maleic anhydride-modified polypropylene (Admer QF500, made by Mitsui Petrochemical Industries, Ltd.).
- the obtained multilayered sheet had a thick-ness construction of outer layer/adhesive layer/intermediate layer/adhesive layer/inner layer of 50/10/50/10/50 (microns).
- the single-layer film and multilayered films thus obtained were tested for dispersibility of montmorillonite, transparency and basal spacing, and OTR, respectively. The results are shown in Table 1.
- Example 1 was repeated except for changing the amount used of montmorillonite and EVOH to 2 parts and 98 parts respectively, to obtain a single-layer film and a multilayered film.
- the thus obtained films were tested in the same manner as in Example 1. The results are shown in Table 1.
- Example 1 was repeated except for changing the amount used of montmorillonite and EVOH to 4 parts and 96 parts respectively, to obtain a single-layer film and a multilayered film.
- the thus obtained films were tested in the same manner as in Example 1. The results are shown in Table 1.
- Example 1 was repeated except that only the EVOH was used, i.e. without montmorillonite, to obtain a single-layer film and a multilayered film, which were tested in the same manner. The results are shown in Table 1.
- Example 1 The same EVOH and montmorillonite as in Example 1 were used. After 98 parts of EVOH and 2 parts of montmorillonite had been mixed well in a Henschel mixer, the mixture was extruded through an extruder at a nozzle temperature of 230°C and a cylinder temperature of 230°C to form pellets. The pellets thus obtained were processed in the same manner as in Example 1 to form a single-layer film and a multilayered film, which were then evaluated in the same manner. The results are shown in Table 1.
- Example 1 The same EVOH as in Example 1 and a commercially available natural talc were used. After 98 parts of EVOH and 2 parts of the talc had been mixed well in a Henschel mixer, the mixture was extruded through an extruder at a nozzle temperature of 230°C and a cylinder temperature of 230°C to form pellets. The pellets thus obtained were processed in the same manner as in Example 1 to form a single-layer film and a multilayered film, which were then evaluated in the same manner. The results are shown in Table 1.
- Example 1 The same EVOH as in Example 1 and a commercially available natural mica (non-water swellable) were used. After 98 parts of EVOH and 2 parts of the mica had been mixed well in a Henschel mixer, the mixture was extruded through an extruder at a nozzle temperature of 230°C and a cylinder temperature of 230°C to form pellets. The pellets thus obtained were processed in the same manner as in Example 1 to form a single-layer film and a multilayered film, which were then evaluated in the same manner. The results are shown in Table 1.
- Example 2 was repeated except for using an EVOH having an ethylene content of 64 mol%, a saponification degree of vinyl acetate component of 99.3 mol% and an MI of 25 g/10 min and changing methyl alcohol in a concentration of 65% by weight to n-propyl alcohol in a concentration of 80% by weight, to obtain a single-layer film and a multilayered film, which were then evaluated in the same manner.
- the results are shown in Table 1.
- Example 2 was repeated except for using an EVOH having an ethylene content of 18 mol%, a saponification degree of vinyl acetate component of 99.4 mol% and an MI of 25 g/10 min and changing the concentration of methyl alcohol to 45% by weight, to obtain a single-layer film and a multilayered film, which were then evaluated in the same manner.
- the results are shown in Table 1.
- Comparative Example 2 was repeated except for using bentonite instead of montmorillonite, to obtain a single-layer film and a multilayered film, which were then evaluated in the same manner. The results are shown in Table 1.
- Example 1 The mixed liquid of montmorillonite and EVOH (containing water/methanol) obtained in Example 1 was laminated by glavure coating on the surface of a polypropylene film having been provided with an anchor layer by coating polyurethane resin and then dried to obtain a multilayered film.
- the coating layer of the obtained film was evaluated for gas barrier property, dispersibility of montmorillonite and transparency. The results are shown in Table 1.
- the basal spacing was determined as follows. A multilayered film was separately prepared by coating the mixed liquid on the surface of the same polypropylene film but without the anchor layer, followed by drying. The coating layer was then peeled off and subjected to test for basal spacing. The result is shown in Table 1.
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Claims (4)
- Harzmasse, umfassend ein Ethylen-Vinylalkohol-Copolymer (EVOH) mit einem Ethylengehalt von 20 bis 60 Mol% und ein wasserquellbares Phyllosilikat, wobei das wasserquellbare Phyllosilikat im EVOH mit einem Basisabstand dispergiert ist, der die folgende Bedingung (I) erfüllt
- Verfahren zur Herstellung einer Harzmasse, umfassend Mischen von EVOH mit einem Ethylengehalt von 20 bis 60 Mol% und einem wasserquellbaren Phyllosilikat in Gegenwart von Wasser und anschließendes Trocknen des Gemischs.
- Wässerige Mischung, die als Hauptbestandteile EVOH mit einem Ethylengehalt von 20 bis 60 Mol%, ein wasserquellbares Phyllosilikat und Wasser enthält.
- Mehrschichtige Struktur, umfassend wenigstens eine Schicht der Harzmasse nach Anspruch 1.
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JP25370690 | 1990-09-21 | ||
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DE3806548C2 (de) * | 1987-03-04 | 1996-10-02 | Toyoda Chuo Kenkyusho Kk | Verbundmaterial und Verfahren zu dessen Herstellung |
CA1335424C (en) * | 1987-12-29 | 1995-05-02 | Tohei Moritani | Multilayered packaging materials having high gas barrier property |
AU616730B2 (en) * | 1988-02-29 | 1991-11-07 | Kuraray Co., Ltd. | Multilayered container |
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1991
- 1991-09-17 EP EP91115737A patent/EP0479031B1/de not_active Expired - Lifetime
- 1991-09-17 DE DE69123536T patent/DE69123536T2/de not_active Expired - Lifetime
-
1993
- 1993-10-21 US US08/140,263 patent/US5428094A/en not_active Expired - Lifetime
Patent Citations (1)
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EP0301878A1 (de) * | 1987-07-30 | 1989-02-01 | E.I. Du Pont De Nemours And Company | Äthylen-Vinylalkohol-Kopolymere mit plättchenförmigen Glimmerfüllstoffen, Verfahren für die Herstellung derselben und Mehrschichtbehälter mit daraus hergestellten Schichten |
Non-Patent Citations (1)
Title |
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6391449B1 (en) | 1998-12-07 | 2002-05-21 | Amcol International Corporation | Polymer/clay intercalates, exfoliates, and nanocomposites comprising a clay mixture and a process for making same |
US6407155B1 (en) | 2000-03-01 | 2002-06-18 | Amcol International Corporation | Intercalates formed via coupling agent-reaction and onium ion-intercalation pre-treatment of layered material for polymer intercalation |
US6462122B1 (en) | 2000-03-01 | 2002-10-08 | Amcol International Corporation | Intercalates formed with polypropylene/maleic anhydride-modified polypropylene intercalants |
US6632868B2 (en) | 2000-03-01 | 2003-10-14 | Amcol International Corporation | Intercalates formed with polypropylene/maleic anhydride-modified polypropylene intercalants |
US6596803B2 (en) | 2000-05-30 | 2003-07-22 | Amcol International Corporation | Layered clay intercalates and exfoliates having a low quartz content |
Also Published As
Publication number | Publication date |
---|---|
DE69123536T2 (de) | 1997-05-15 |
DE69123536D1 (de) | 1997-01-23 |
US5428094A (en) | 1995-06-27 |
EP0479031A1 (de) | 1992-04-08 |
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